CN109643081A - Metallization includes the method for the optical element of surface relief structure - Google Patents
Metallization includes the method for the optical element of surface relief structure Download PDFInfo
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- CN109643081A CN109643081A CN201780034154.4A CN201780034154A CN109643081A CN 109643081 A CN109643081 A CN 109643081A CN 201780034154 A CN201780034154 A CN 201780034154A CN 109643081 A CN109643081 A CN 109643081A
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- Prior art keywords
- metal
- surface relief
- printing
- optical element
- relief structure
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- 238000000034 method Methods 0.000 title claims abstract description 88
- 230000003287 optical effect Effects 0.000 title claims abstract description 45
- 238000001465 metallisation Methods 0.000 title description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 84
- 239000002184 metal Substances 0.000 claims abstract description 82
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 3
- 238000007639 printing Methods 0.000 claims description 53
- 238000000576 coating method Methods 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 34
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 25
- 239000004744 fabric Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 9
- 238000007641 inkjet printing Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000443 aerosol Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims 1
- 239000000976 ink Substances 0.000 description 46
- 239000010410 layer Substances 0.000 description 20
- 239000000758 substrate Substances 0.000 description 18
- 239000002086 nanomaterial Substances 0.000 description 17
- 239000000523 sample Substances 0.000 description 17
- 238000001093 holography Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 102220043159 rs587780996 Human genes 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H1/024—Hologram nature or properties
- G03H1/0244—Surface relief holograms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/328—Diffraction gratings; Holograms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H1/0252—Laminate comprising a hologram layer
- G03H1/0256—Laminate comprising a hologram layer having specific functional layer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2250/00—Laminate comprising a hologram layer
- G03H2250/36—Conform enhancement layer
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Holo Graphy (AREA)
Abstract
Provide a kind of method that metal structure is formed on the optical element for including surface relief structure, this method comprises: metalliferous ink (14) is coated to the surface relief structure (12) to form the metal structure, wherein the metalliferous ink includes one or more organic solvents and as follows one or more: uniform soluble metal salt；Metal complex；Or size is less than the metal nanoparticle of 50nm.
Description
The present invention relates to the methods and apparatus that metallization includes the optical element of surface relief structure.More specifically, this hair
It is bright to be related to using the metallic ink metallization comprising metal salt, metal complex and/or nano particle including surface relief structure
Optical element method and apparatus.
The technology of metalized surface relief fabric is many institute's weeks in the optically variable device field of such as banknote and credit card
Know.In both cases, which is all based on the offline process that the whole surface of wherein structuring foil is metallized.Permitted
In more situations/application in, this metallized foils containing Difraction surface relief fabric then pass through chemistry route and are partly gone
Metallization.It should be appreciated that such process is time-consuming and can generate sizable waste.
Other methods of diffraction efficiency for enhancing surface relief grating include depositing one or more layers to have high refraction
The modification of the transparent dielectric of rate, the transparent dielectric are usually made of refractory material, such as: TiO2、HfO2、ZrO2、Ta2O5
And ZnS.All these substances usually have the refractive index within the scope of 2.0-2.3.It is most of for polymerizeing in these materials
Security printing on object foil, the polymer foil pass through various vacuum deposition methods before or after embossing or moulding technology
Coating.
Therefore, this field becomes known for carrying out high-test metal to the optical element for including surface relief structure there are this kind of
The technical problem that the method for change is limited in terms of output and manufacture flexibility.The present invention is dedicated to solving in one aspect above-mentioned
Problem.
According to the first aspect of the invention, provide it is a kind of include surface relief structure optical element on form metal
The method of structure is coated to this method comprises: will contain metallic ink to form the metal structure in the surface relief structure,
It include wherein one or more organic solvents and as follows one or more containing metallic ink: uniform soluble metal salt；Gold
Belong to complex compound；Or size is less than the metal nanoparticle of 50nm.
In one embodiment, the metal or include metal or metal ion selected from the group below containing metal component: silver,
Gold, copper, ruthenium, osmium, iridium and platinum.
In one embodiment, the metal or containing metal component include silver or silver ion.
In one embodiment, the solvent or every kind of solvent are selected from the group: alcohol, ester, ketone, glycol ether or phenolic ether.
In one embodiment, the surface tension of at least one solvent is less than or equal to 25dyn/cm (dynes per centimeter).
In one embodiment, the surface tension of at least one solvent is greater than or equal to 30dyn/cm.
In one embodiment, the metal structure is in one or more dimensions with the size between 10-500nm.
In one embodiment, the metal structure is in one or more dimensions with the size between 20-100nm.
In one embodiment, the metal structure is in one or more dimensions with the size between 20-50nm.
In one embodiment, the metal structure has >=1 optical density.
In one embodiment, the metal structure has optical density of the range in 1 to 6.
In one embodiment, the metal structure has optical density of the range in 2 to 4.
In one embodiment, the applying step includes printing in the surface relief structure of the optical element
Or coating contains metallic ink.
In one embodiment, the print steps include following one or more: printed on line (inline
Printing), on-demand printing (on demond printing) or registration printing (in-register printing).
In one embodiment, the printing or coating include as follows one or more: dispensing (dispensing), spray
It is ink print, aerosol injection, hectographic printing, silk-screen printing, bat printing, intaglio printing, flexible version printing, stencilization, coining, quiet
Reply print or lithographic printing by cable.
In one embodiment, the surface relief structure includes the surface texture for limiting multiple peak and valleys, and wherein
The metal structure is completely covered the peak of the surface relief structure and is filled up completely the paddy between peak.
In one embodiment, the surface relief structure includes the surface texture for limiting multiple peak and valleys, and wherein
The metal structure limits conformal coating in the peak and valley of the surface relief structure.
In one embodiment, the surface relief structure is had and the surface undulation knot by partially metallised to limit
The partially metallised structure of the identical pitch of structure.
In one embodiment, after the applying step, the method also includes dry described containing metallic ink
Step.
In one embodiment, the drying steps are executed so that the coated temperature containing metallic ink is in 80-300
Within the temperature range of DEG C.
In one embodiment, the drying steps are executed so that the coated temperature 120-180 containing metallic ink
Within the temperature range of DEG C.
In one embodiment, the drying steps were performed less than 5 minutes.
In one embodiment, the drying steps were performed less than 1 minute.
In one embodiment, the method also includes being coated to the metal structure for coating or foil.
In one embodiment, the optical element includes following one or more: Difraction surface relief fabric；It returns
Reflect (retro-reflective) surface relief structure；Plasma surface relief fabric.
In one embodiment, the optical element can be operated to generate schemochrome.
In one embodiment, the optical element includes photoelectric device.
According to the second aspect of the invention, a kind of optical element is provided, including passes through any one of preceding claims
The metalized surface relief fabric that the method is formed.
In one embodiment, the optical element includes following one or more: Difraction surface relief fabric；It returns
Reflecting surface relief fabric；Plasma surface relief fabric.
In one embodiment, the optical element can be operated to generate schemochrome.
In one embodiment, the optical element includes photoelectric device.
According to an aspect of the invention, there is provided a kind of formed in surface relief structure by coating containing metallic ink
The method of metal nano dimensional structure.
In one embodiment, the coating method is for applying containing metallic ink to generate metal in surface undulation
The printing or coating method of nano-scale structure.
In one embodiment, the coating method is for applying containing metallic ink in surface relief diffractive structure
Metal nano dimensional structure is generated to enhance the printing or coating method of phase-modulation.
In one embodiment, the printing process is online, or on-demand or register, or more than
All combinations.
According to an aspect of the invention, there is provided a kind of metal nano ruler as described in any one of the preceding claims
Very little structure, including any of metallic element.
In one embodiment, described to contain metallic element containing metallic ink, as uniform soluble salt, metal complex
Or nanoparticle exists.
In one embodiment, the metal is silver.
In one embodiment, described to may be preferable for the suitable of the printing surface relief diffractive structure containing metallic ink
When deposition, wetting, drying and adherency, including one or more solvents are to obtain required viscosity, solid supported, stability and drying
Property, wherein solvent of preferably at least one surface tension less than 25dyn/cm and at least one surface tension are greater than 30dyn/cm
Other solvents combination.
In one embodiment, the solvent used is alcohol, ester, ketone, glycol ether and phenolic ether.
In one embodiment, the Difraction surface relief fabric is completely filled (ginseng and being printed with printing ink
See Fig. 3), wherein the ink be perhaps partly made of uniform soluble metal salt or metal complex or partly by
Nano particle of the size less than or equal to 50nm forms.
In one embodiment, metal conformal coating is formed on the Difraction surface relief fabric.
In one embodiment, metal deposit is carried out to the Difraction surface relief fabric, had and the table to obtain
The partially metallised structure of face relief fabric same pitch.
In one embodiment, the method can be operated to prepare in one or more dimensions having a size of 10-500nm,
Preferred size is 20-100nm, more preferably having a size of the metallization structure of 20-50nm.
In one embodiment, the method can be used for preparing in one or more dimensions having a size of 1-500nm, preferably ruler
Very little is 2-100nm, more preferably having a size of the metallization structure of 2-50nm.
In one embodiment, by dispensing, ink jet printing, aerosol injection, hectographic printing, silk-screen printing, bat printing, recessed
Version printing, flexible version printing, stencilization, coining, xerography or offset printing are printed or are coated.
In one embodiment, the method for executing the dry printing ink, wherein the temperature of ink is at 80-300 DEG C
In temperature range, preferably within the temperature range of 120-180 DEG C, and drying time less than 5 minutes, preferably smaller than 1 minute.
In one embodiment, the deposition method is on-demand and convenient for change, such as ink jet printing in operation.
In one embodiment, the metal structure by covering metal structure another material protection, such as coating or
Foil.
Detailed description of the present invention embodiment with reference to the drawings, in which:
Fig. 1 shows a kind of illustrative methods according to an embodiment of the present invention；
Fig. 2 to 4 shows the optical element including the metalized surface relief fabric manufactured according to embodiments of the present invention
Different modifications；And
Fig. 5 shows the scanning of the optical element including the metalized surface relief fabric formed according to embodiments of the present invention
Electron micrograph (SEM).
In some respects, the present invention provides by directly increasing material (additive) printing process to any nanometer or micro- knot
The method of structure surface coating metal coating.Another aspect of the present invention is that being formed by metal coating makes coated nanometer
Or micro-structure has the increasing of the specular reflective of height or the phase-modulation of reflected light, desired color or required electrical properties
By force or combinations of the above.
Operating method of the invention is described referring now to Fig. 1.Fig. 1 shows the one of non-limiting embodiment of the invention
As flow chart.
Step 100: sample substrate is provided
The embodiment of the present invention is related to enhancing Difraction surface relief fabric.Exemplary diffraction surface relief structure can be such as
For the grating and optical authentication device of spectrometer, such as a part of credit card and banknote.Surface undulation nanometer and micro-structure
Diffraction effect be well-known in optics circle.These structures have very big business and technical meaning, because they can be with
It is easy to be mass produced duplication using various embossing and casting technique based on thermosetting property or photo-curing material.For example, can be with
It is used as described in EP 1150843B1Method.However, the type of Difraction surface relief fabric, form and opening up
It flutters structure and manufacturing method is not important for the purpose of the present invention, no longer further discuss here.
This method proceeds to step 102.
Step 102: providing and contain metallic ink
Inventors of the present invention have surprisingly found that various industrial printing processes can be used.In embodiments, can make
With one group of specific commercial silver-base metal ink.It is also possible, however, to use other suitable metals.
In non-limiting embodiment, these inks are prepared again to obtain desirable properties of the invention.Applicable print
Brush and the non-limiting specific example of coating method are: ink-jet, intaglio printing, flexographic printing and slot coated.
Inventor has found that the preferred form containing metallic ink for the purpose of the present invention including wherein metal with metal
It is that salt or metal complex are presented or containing metallic ink be wherein the homogeneous liquid based on particle.Metal salt or metal complex
Need to dissolve in one or more organic solvents.The typical case of suitable metal salt or metal complex can in US 7,955,
It is found in 528.However, the non-limitative example for being suitable for the invention metal or metal ion include: silver, gold, copper, ruthenium, osmium,
Iridium and platinum.The non-limitative example of suitable ligand for metal complex can be carbamate.
As an alternative, ink includes most of lower than 50nm and preferred if metalliferous ink is based on particle
Particle lower than 10nm, so as to form the conformal continuous coated of the final metal coating of 10-100nm for nanostructure.Non-
In limitative examples, about 50% or more particle size is less than 50nm, preferably smaller than 10nm.
For preparing again, solvent is needed to keep stability of ink and shelf-life when dry by distinct methods, can
The silver content of formula is reduced under the requirement of printing and film forming characteristics.According to the ink to prepare again, the printing process used
(described below) and drying means (described below) and the adhesive force of printed layer etc., can find out solvent appropriate or molten
Agent composition.For this purpose, preferred compound is the typical organic solvents for ink, such as alcohol, ester, ketone, glycol ether
And phenolic ether.Again preparing and generating viscosity is 0.5-100cP, the preferably mixture of 1-50cP.
This method proceeds to step 104.
Step 104: deposited metal layer
In order to promote diffraction efficiency, is usually coated by all standing metal and thin metal coating is coated to optical grating construction.Gold
Belong to layer and increase the refractive index of surface undulation, to also enhance phase-modulation.If additional polymer coating is coated to
On the metal layer, then the additional polymeric layer is also used as protective layer, such as the protection structure for preventing forgery.
It is preferable to use carry out on-demand printed on line or coating containing metallic ink described in step 102 to apply for metal structure
It applies, to generate metal nano dimensional structure in surface relief structure, to enhance phase-modulation.
In embodiments, it is expected that metal coating is conformal and uniform shallow layer, so that surface nano-structure is completely simultaneously
And there are the diffractive properties of enhancing after application.In embodiments, metal coating can be applied by industrial printing processes, with
It is directly integrated with the known printing process based on continuous net.
In embodiments, it may include following one or more for printing or coating: dispensing, ink jet printing, aerosol spray
It penetrates, hectographic printing, silk-screen printing, bat printing, intaglio printing, flexible version printing, stencilization, coining, xerography or plate print
Brush.
Desired effect is that the surface relief structure is made to have height mirror surface anti-in observation surface relief structure downwards
Penetrating property, or the phase-modulation of reflected light significantly increases when being observed by substrate.
Different configurations as shown in Figures 2 to 4 can be used.Fig. 2 to Fig. 4 shows load-bearing surface fluctuating 12 and metal coating
14 substrate 10.Coating 14 can be conformal (as shown in Figure 2), is partially filled with (as shown in Figure 3) or fill up entire grating knot
Structure (as shown in Figure 4).
This method proceeds to step 106.
Step 106: dry and solidified sample
In embodiments, can optionally be dried and/or be solidified can be between 50 DEG C to 250 DEG C for printed metal layer
At a temperature of, preferably carried out between 100 DEG C to 200 DEG C.In other embodiments, dry and/or solidification can be at 80 DEG C -300
Between DEG C, preferably 120-180 DEG C progress.1 to 5 minute preferred time ruler can be used.
This method proceeds to step 108.
Step 108: coating protective coating
It is alternatively possible to which protective foil or coating are coated on metalized surface surface relief grating.
The following exemplary embodiment of the method for the present invention will be illustrated with reference to lower example 1 to 8.In each case, this hair
Bright method all generates the metallization optical element of high quality.Exemplary optical element may include diffraction, nanometer or micro-structural
Surface, holographic and/or other surfaces provide schemochrome surface while using rapidly and effectively manufacturing method.As
Additional or replacement, these metal surfaces can also show height reflex reflection and reflecting attribute.
Example 1
By Cabot (Cabot) ink CMI 300 (Cabot Co., Ltd, the U.S.), the stable silver nano-grain base of 0.4ml
The Dowanol methyl of ink and 0.2ml(carbitol) mixing.Use the Dimatix with 10pL print head
2831 with 20 microns of drop spacing by the mixture ink jet printing to made of UV resin it is open holography nanostructure on,
The nanostructure passes throughMethod is prepared in OPP film substrate.The sample of printing is transparent and appearance is omited
Band yellow.The sample of printing is solidified 5 minutes in 130 DEG C of baking oven.Obtained sample is seeing down into the open holography
Bright and high reflectivity metalized holographic figure is shown when structure, shows the diffraction from prototype structure in reflected intensity side
Face is greatly enlarged.Using backlight, the image of printing is shown as navy blue, this together illustrates surface holography with above-mentioned observation result
With a thickness of conformal, the continuous and uniform silverskin of about 30-50nm on figure.
Example 2
It must by the Liquid X (Liquid X type metal company, the U.S.) and the Dowanol methyl card of 0.4ml of 0.8ml
Alcohol mixing.The mixture ink jet printing is arrived with 20 microns of drop spacing using the Dimatix 2831 with 10pL print head
In the open holography nanostructure made of UV resin, the nanostructure passes throughMethod is in OPP film base
It is prepared on bottom.The sample of printing is transparent, and in appearance without apparent color.By the sample of printing at 130 DEG C
Solidify 5 minutes in baking oven.Resulting sample shows bright and high reflectivity metalized holographic figure, shows from original knot
The diffraction of structure is greatly enlarged in terms of reflected intensity.Using backlight, the image of printing has green tone.
Example 3
The Dowanol methyl carbitol of the Inktec CO-011 ink (Inktec, South Korea) of 0.8ml and 0.4ml is mixed
It closes.Using the Dimatix 2831 with 10pL print head with 20 microns of drop spacing by the mixture ink jet printing to by UV
In open holography nanostructure made of resin, the nanostructure passes throughMethod is in OPP film substrate
Preparation.The sample of printing is transparent, and in appearance without apparent color.Baking oven by the sample of printing at 130 DEG C
Middle solidification 5 minutes.Resulting sample shows bright and high reflectivity metalized holographic figure, shows from prototype structure
Diffraction is greatly enlarged in terms of reflected intensity.
Example 4
Passing throughThe open holography nanometer made of UV resin that method is prepared in OPP film substrate
In structure, with 4 microns of k sticks (k-bar scrapes inker) D50=70nm coated nanoparticles silver ink water Sicrys I50T-13
(PVnanoCell, Israel).Sample is solidified 5 minutes at 130 DEG C.Before showing approximate 100nm and being averaged silver thickness
After weigh basilar memebrane.Resulting sample is displayed without diffraction when the open surface for seeing down into coating rises and falls.However, through holding
Carry the substrate observation of hologram, it is seen that the diffraction of the reflected intensity amplification from prototype structure.
Example 5
Passing throughThe open holography nanometer made of UV resin that method is prepared in OPP film substrate
In structure, 66mg nano particle silver ink water Sicrys I50T-13 (PVnanoCell, with color is coated with 4 microns of k sticks (k-bar)
Column) and 57mg Dowanol DPnB mixture.Sample is solidified 5 minutes at 130 DEG C.According to calculating, average silver thickness
It is about 50nm.Obtained sample shows some diffraction in the open surface undulation for seeing down into the coating, but is less than not
The reference substance of coating.However, seeing the diffraction from prototype structure in reflected intensity side through the substrate observation of carrying hologram
Face is greatly enlarged.
Example 6
Use the Inktec TEC-PR-010 ink (Inktec, South Korea) and 5-95% (body for containing 5-95% (volume)
Product) solvent or solvent mixture multicomponent ink.The metal-containing solutions layer is arrived with Polaris PQ-512 ink jet printing
In the open holography nanostructure made of UV resin, the nanostructure passes throughMethod is in PET film base
It is prepared on bottom.Ink is solidified 10 minutes at 160 DEG C, bright and strong reflection metal layer is generated, shows original fluctuating
The diffraction of structure dramatically increases, and the reflected intensity of the structure is greatly enlarged.
Example 7
Use the Inktec TEC-CO-011 ink (Inktec, South Korea) and 5-95% (body for containing 5-95% (volume)
Product) itself containing one or more ingredients solvent multicomponent ink.The metal-containing solutions layer is coated to by UV resin
In manufactured open holographic nanostructure, the nanostructure passes throughMethod is prepared in PET film substrate.
The metallic ink is deposited on this structure using Polaris PQ-512 ink jet printing head.By the liquid ink water layer 160
Solidify 10 minutes at DEG C, generates bright and strong reflection metal layer, show that the diffraction of original relief fabric dramatically increases, and
And the reflected intensity of the structure is greatly enlarged.
Example 8
Passing throughThe open holography nanometer made of UV resin that method is prepared in OPP film substrate
In structure, with 4 microns of k stick (k-bar) D50=70nm coated nanoparticles silver ink water Sicrys I50T-13 (PVnanoCell,
Israel).
Metal film is coated to (nanostructure passes through in the substrate of holography nanostructure made of UV resinMethod is prepared in PET film substrate), then by using Adphos MPP-120 lamp (Adphos group, moral
State) continue the wet metal film of the solidification of photodissociation in 0.001 to 2 seconds between 50% to 100%.Solidify the metal for generating bright and strong reflection
Layer, shows that the diffraction of original relief fabric dramatically increases, and the reflected intensity of the structure is greatly enlarged.
The advantages of can see the method for the present invention in Fig. 5.Fig. 5 shows the scanning electron microscopy of Ag metallization diffraction grating
Mirror (SEM) figure.The flute density of grating is about 1400 lines/mm.It usesTechnology is by grating replication to PET foil
On.Duplicate is using made of the photo curable acrylate based resin of X-29 from Stensborg A/S.
Show the surface undulation metal layer obtained using CO-011.Silver metal layer is located at surface undulation as conformal coating
Top.In the case where silver layer is not present, which is removed by ultra-soft high viscosity adhesive tape.As shown, whole surface has
Flat (even), metal layer that is smooth and being uniformly distributed (well-distributed).
Following embodiment is not belonging to the scope of the present invention, and for illustrating the method for the present invention changing relative to known method
Into.
Example 9
Passing throughThe open holography nanometer made of UV resin that method is prepared in OPP film substrate
In structure, 3 kinds different metal gravure plate ink Eckhart (Germany): Ultrastar are coated with 4 microns of k sticks (k-bar)
GX2561, Ultrastar FX-1604 and Ultrastar GX-2807.Metal component is having a size of 6-8 microns and thickness is less than
The aluminum slice of 100nm.Sample is 2 minutes dry at 70 DEG C.For all samples, open table is seen down into from prototype structure
The diffraction efficiency of face relief fabric does not enhance, but the substrate for penetrating the carrying surface relief structure observes faint increasing
By force.In these cases, effect is far below reflected intensity greatly enlarged seen in example 1-3.
Example 10
The open holography nanostructure made of UV resin, passes throughMethod makes in PET film substrate
Conductive ink water-color paintbrush (Circuit Scribe Conductive Ink is drawn with the circuit from Electroninks (U.S.)
Pen) 1 Ω/cm is drawn.For all samples, when see open surface directly down or from top at any angle from when,
The feature of original relief fabric can not be identified.Sample is kept to towards light source and is penetrated the reverse side of substrate observation relief fabric
When, the enhancing of hologram is not observed.
As described above, contain metallic ink the present invention provides a kind of on-demand printed on line or coating, the dry ink with
Generate the element containing optics of metals with nano-scale structure (for example, surface relief diffractive structure for enhancing phase-modulation)
Method.
In this way, the present invention can be realized the nanometer of manufacture metallization and the completely new technique of micro-structure, whole or portion are used
Point register (in-register), printed on line, and be cost-efficient.This metalliferous nanometer and micro-structure can
To be, for example, to be used for retroreflecting (retro-reflective) purpose and spectrum purposes.The metallization process system can be used
Another example for the optical module made is the wavelength (de) multiplexing component used in telecommunications application.
In addition, by the ability that ink-jet coats metallic nanotubes coating on demand to polymeric substrates creation is had etc.
The layer of gas ions attribute is possibly realized.Shown already this plasmasphere can control soild state transmitter transmitting light (such as
Direction and polarization) and the coupling efficiency of solar battery can be enhanced.It has also been found that surface plasma can be used for itself or with spread out
It penetrates structure combination and generates schemochrome.Using method described in present patent application, can be manufactured in online (in-line) technique
Structure with above-mentioned attribute, without expensive offline (off-line) vacuum deposition device.
Another application for applying metallic nanotubes coating on demand by ink-jet is the optical bio based on monolithic optical waveguide
Sensor.This waveguide is usually required using refractory material, only for example, such as TiO2、HfO2、ZrO2、Ta2O5With ZnS etc..Institute
Having these substances usually has the refractive index in the section 2.0-2.3.This is that waveguide connects with the biological sample usually with high-moisture
Typical refractive range needed for touching operation.Itd is proposed metallic nanotubes coating is used, makes it possible to realize in online process
Use to these materials for usually requiring expensive offline process, consequently facilitating manufacture disposable optical biosensor.With
In the use of metallic nanotubes coating being to be easy to know molecular pattern on the other hand in the optical waveguide of the sensing based on evanescent field
The suitable layers of (compatible reaction) are not fixed on the layer.
It the composite can be widely applied to holographic printing, holographic embossing, optical sensor, solar battery, TFT-LCD (film
Transistor liquid crystal display (TFT-LCD)), OLED (Organic Light Emitting Diode), the fields such as flexible display.Those skilled in the art will manage
Solution, aforementioned disclosed concept and specific embodiment can be easily used as modifying or designed for realizing the identical mesh of the present invention
Other embodiments basis.It will also be appreciated by those of skill in the art that these equivalent embodiments are without departing from appended
The spirit and scope of the present invention illustrated in claim.
Specifically various embodiments of the present invention were described in reference example already.Although being shown in the attached drawings specific
It example and is described in detail, it should be understood that, these attached drawings and detailed description are not intended to send out this
It is bright to be limited in disclosed concrete form.Will understand that the embodiment that describes within the scope of the present invention carry out various change and
Modification.
Claims (31)
1. a kind of method that metal structure is formed on the optical element for including surface relief structure, this method comprises:
Metallic ink will be contained and be coated to the surface relief structure to form the metal structure, wherein the packet containing metallic ink
Containing one or more organic solvents and as follows one or more: uniform soluble metal salt；Metal complex；Or size is small
In the metal nanoparticle of 50nm.
2. according to the method described in claim 1, wherein, the metal or include metal or gold selected from the group below containing metal component
Belong to ion: silver, gold, copper, ruthenium, osmium, iridium and platinum.
3. according to the method described in claim 2, wherein, the metal or include silver or silver ion containing metal component.
4. method according to claim 1,2 or 3, wherein the solvent or every kind of solvent are selected from the group: alcohol, ester, ketone,
Glycol ether or phenolic ether.
5. method according to any of the preceding claims, wherein the surface tension of at least one solvent is less than or waits
In 25dyn/cm.
6. method according to any of the preceding claims, wherein the surface tension of at least one solvent is greater than or waits
In 30dyn/cm.
7. method according to any of the preceding claims, wherein the metal structure is in one or more dimensions
With the size between 10-500nm.
8. according to the method described in claim 7, wherein, the metal structure has 20-100nm in one or more dimensions
Between size.
9. according to the method described in claim 8, wherein, the metal structure has 20-50nm in one or more dimensions
Between size.
10. method according to any of the preceding claims, wherein the metal structure has >=1 optical density.
11. according to the method described in claim 10, wherein, the metal structure has optical density of the range in 1 to 6.
12. according to the method for claim 11, wherein the metal structure has optical density of the range in 2 to 4.
13. method according to any of the preceding claims, wherein the applying step is included in the optical element
The surface relief structure on print or coating is described contains metallic ink.
14. according to the method for claim 13, wherein the print steps include following one or more: online print
Brush, on-demand printing or registration printing.
15. method described in 3 or 14 according to claim 1, wherein the printing or coating include as follows one or more:
Dispensing, ink jet printing, aerosol injection, hectographic printing, silk-screen printing, bat printing, intaglio printing, flexible version printing, stencilization,
Coining, xerography or lithographic printing.
16. method according to any of the preceding claims, wherein the surface relief structure includes limiting multiple peaks
With the surface texture of paddy, and wherein the metal structure peak of the surface relief structure is completely covered and be filled up completely peak it
Between paddy.
17. according to claim 1 to method described in any one of 15, wherein the surface relief structure includes that restriction is multiple
The surface texture of peak and valley, and wherein the metal structure limits conformal painting in the peak and valley of the surface relief structure
Layer.
18. according to claim 1 to method described in any one of 15, wherein the surface relief structure is partially metallised
To limit the partially metallised structure with pitch identical with the surface relief structure.
19. method according to any of the preceding claims, wherein after the applying step, the method also includes
Dry described the step of containing metallic ink.
20. according to the method for claim 19, wherein execute the drying steps so that coated contains metallic ink
Temperature within the temperature range of 80-300 DEG C.
21. according to the method for claim 20, wherein execute the drying steps so that coated contains metallic ink
Temperature within the temperature range of 120-180 DEG C.
22. according to the method for claim 20 or 21, wherein the drying steps were performed less than 5 minutes.
23. according to the method for claim 22, wherein the drying steps were performed less than 1 minute.
24. method according to any of the preceding claims further includes that coating or foil are coated to the metal structure
The step of.
25. method according to any of the preceding claims, wherein the optical element includes following one or more
It is a: Difraction surface relief fabric；Holographic surface relief structure；Retro-reflective surfaces relief fabric；Plasma surface, which rises and falls, to be tied
Structure.
26. method according to any of the preceding claims, wherein the optical element can be operated to generate structure
Color.
27. method according to any of the preceding claims, wherein the optical element includes photoelectric device.
28. a kind of optical element, the metalized surface including being formed by method described in any one of preceding claims is risen
Lie prostrate structure.
29. optical element according to claim 28, wherein the optical element includes following one or more: diffraction
Surface relief structure；Holographic surface relief structure；Retro-reflective surfaces relief fabric；Plasma surface relief fabric.
30. the optical element according to claim 28 or 29, wherein the optical element can be operated to generate schemochrome.
31. according to optical element described in claim 28,29 or 30, wherein the optical element includes photoelectric device.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA201600327 | 2016-06-03 | ||
| DKPA201600327 | 2016-06-03 | ||
| PCT/EP2017/062724 WO2017207420A1 (en) | 2016-06-03 | 2017-05-25 | Method of metallising optical elements comprising surface relief structures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109643081A true CN109643081A (en) | 2019-04-16 |
Family
ID=58992840
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780034154.4A Pending CN109643081A (en) | 2016-06-03 | 2017-05-25 | Metallization includes the method for the optical element of surface relief structure |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US11029647B2 (en) |
| EP (1) | EP3465353A1 (en) |
| CN (1) | CN109643081A (en) |
| WO (1) | WO2017207420A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111179734A (en) * | 2020-01-16 | 2020-05-19 | 深圳市金质金银珠宝检验研究中心有限公司 | Method for realizing reflective volume holographic color three-dimensional anti-counterfeiting |
| CN111258199A (en) * | 2020-01-16 | 2020-06-09 | 深圳市金质金银珠宝检验研究中心有限公司 | Method for realizing reflective volume holographic three-dimensional anti-counterfeiting based on physical interference |
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|---|---|---|---|---|
| KR20180028791A (en) * | 2016-09-09 | 2018-03-19 | 삼성전자주식회사 | Phase modulation active device, method of driving the same and optical apparatus including the phase modulation active device |
| US10350935B1 (en) | 2018-01-10 | 2019-07-16 | Assa Abloy Ab | Secure document having image established with metal complex ink |
| US10821765B2 (en) | 2018-01-10 | 2020-11-03 | Assa Abloy Ab | Secure documents and methods of manufacturing the same |
| CN108922374B (en) * | 2018-07-17 | 2020-12-18 | 中国科学院光电技术研究所 | Sub-wavelength structure for realizing structural color and holographic double anti-counterfeiting |
| CN109291673B (en) * | 2018-09-25 | 2020-08-11 | 武汉华工图像技术开发有限公司 | Accurately aluminized patterned holographic anti-counterfeiting device and preparation method thereof |
| DE102022103994A1 (en) | 2021-03-17 | 2022-09-22 | Heidelberger Druckmaschinen Aktiengesellschaft | Process for producing imaging structures |
| US20230375759A1 (en) * | 2022-05-18 | 2023-11-23 | GE Precision Healthcare LLC | Aligned and stacked high-aspect ratio metallized structures |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3465353A1 (en) | 2019-04-10 |
| US20190212697A1 (en) | 2019-07-11 |
| US11029647B2 (en) | 2021-06-08 |
| WO2017207420A1 (en) | 2017-12-07 |
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